efficient synthesis of diarymethane derivatives by pdcl2

1

Supporting Information

Nickel-Promoted C(2)-H Amidation of Quinoline N-

oxides with N-Fluorobenzenesulfonimide

Shuaijun Han,a Xianying Gao,a Qingsong Wu,a Jingya Li,b Dapeng Zou,*, a Yusheng Wu,*, a, b, c and Yangjie Wu*, a

a The College of Chemistry and Molecular Engineering, Henan Key Laboratory of Chemical Biology and Organic Chemistry, Zhengzhou University, Zhengzhou, People’s Republic of China Fax: (+86)-371-6776-3390; phone: (+86)-371-6776-6865; e-mail: [email protected] or [email protected]

b Tetranov Biopharm, LLC., and Collaborative Innovation Center of New Drug Research and Safety Evaluation, Zhengzhou, 450052, People’s Republic of China

c Tetranov International, Inc., 100 Jersey Avenue, Suite A340, New Brunswick, NJ 08901, USA. Fax: (+ 1)-732-253-7327; phone: (+ 1)-732-253-7326; e-mail: [email protected]

Table of Contents1. General information ...................................................................................................22. Preparation of substrates ............................................................................................23. Optimization of the reaction.......................................................................................2

4. General procedure for the reaction.............................................................................3

5. Control Experiments. .................................................................................................4

6. X-Ray Crystallographic Data of 3a............................................................................4

7. Plausible Mechanism..................................................................................................68. Characterization data of the products.........................................................................69. References ................................................................................................................1410. 1H NMR and 13C NMR spectra of the products .....................................................15

Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers.This journal is © the Partner Organisations 2019

2

1. General information

All manipulations were performed in 25 mL Schlenk tube equipped with a

magnetic stir bar unless otherwise noted. Solvents and reagents were purchased from

commercial sources and used as received. Flash column chromatography was

performed using silica gel (60-Å pore size, 32-63 µm, standard grade). Analytical

thin-layer chromatography was performed using glass plates pre-coated with 0.25 mm

230-400 mesh silica gel impregnated with a fluorescent indicator (254 nm). Melting

points were recorded by XT4A micro melting point Measurement Instruments,

thermometer was unrevised. The transformation progress and mass spectra were

indicated by GC (Shimadzu GC-2010 Plus) or GC-MS (Thermo Fisher Scientific

DSQ II). NMR spectra were obtained on Bruker AVANCE III systems using CDCl3

or DMSO-d6 as solvent, TMS as internal standard substance, at 400 MHz for 1H NMR,

100 MHz for 13C NMR, and 376 MHz for 19F NMR. The high resolution mass

spectrum was received via Agilent Technologies 6540 UHD Accurate-mass Q-Tof

LC/MS, with ESI as ion source. X-ray analysis was performed with a single-crystal

X-ray diffractometer. Preparative TLC was performed on silica gel plates and

developed with ethyl acetate/hexane.

2. Preparation of substrates

All of the quinoline N-oxides were prepared from the corresponding quinolines

according to the reported procedure.1

3. Optimization of the reaction

Table 1 Additive, base and temperature effects on the synthesis of (E)-N-

(quinolin-2(1H)-ylidene)benzenesulfonamide.a

F NSO2Ph

SO2Ph+

NSO2PhN

H

additive (10 mol %)Na2CO3 (2.0 equiv)

solvent, T °C

1a 2 3a

N

O

entry additive solvent base temperature (°C) yield (%)b

3

1 Ni(OAc)2·4H2O CH3CN Na2CO3 90 18

2 Ni(OAc)2·4H2O DMF Na2CO3 90 81

3 Ni(OAc)2·4H2O DME Na2CO3 90 40

4 Ni(OAc)2·4H2O toluene Na2CO3 90 16

5 NiCl2·6H2O DMF Na2CO3 90 27

6 Ni(acac)2 DMF Na2CO3 90 62

7 Ni(OTf)2 DMF Na2CO3 90 64

8 Ni(PPh3)Cl2 DMF Na2CO3 90 15

9 CuI DMF Na2CO3 90 6710 FeCl2 DMF Na2CO3 90 2211c Ni(OAc)2·4H2O DMF Na2CO3 90 77

12d Ni(OAc)2·4H2O DMF Na2CO3 90 75

13 - DMF Na2CO3 90 49

14 Ni(OAc)2·4H2O DMF K2CO3 90 35

15 Ni(OAc)2·4H2O DMF Cs2CO3 90 25

16 Ni(OAc)2·4H2O DMF K3PO4 90 63

17 Ni(OAc)2·4H2O DMF NaOH 90 72

18 Ni(OAc)2·4H2O DMF - 90 nd

19 Ni(OAc)2·4H2O DMF Na2CO3 50 82 (77)



22 FeCl3 DMF Na2CO3 50 1023 MgCl2 DMF Na2CO3 50 1424 ZnCl2 DMF Na2CO3 50 22

aReaction conditions: 1a (0.3 mmol), 2 (0.6 mmol), additive (10 mol %), base (2 equiv), solvent (2 mL) at 90 °C for 12 h. nd = not detected. bHPLC yields, isolated yields are shown in parentheses. cNi(OAc)2·4H2O (5 mol %). dNi(OAc)2·4H2O (3 mol %).

4. General procedure for the reaction

F NSO2Ph

SO2Ph+

NSO2PhN

H

Ni(OAc)2•4H2O (10 mol %)Na2CO3 (2.0 equiv)

DMF, 50 °C

1 2 3

N

O

R R

4

Experimental Procedure: A dried 25 mL Schlenk tube equipped with a magnetic stir

bar was charged with 1 (0.3 mmol, 1.0 equiv), 2 (0.6 mmol, 2.0 equiv),

Ni(OAc)2·4H2O (10 mol %), Na2CO3 (2.0 equiv), DMF (2.0 mL). Subsequently, the

tube was sealed and the resulting mixture was then stirred at 50 ℃ for 12 h. The crude

production was diluted with ethyl acetate and H2O and then the resulting mixture was

filtered through a pad of Celite. The filtrate was extracted with ethyl acetate (3 × 10

mL). The combined organic layers dried over anhydrous Na2SO4, concentrated in

vacuo, and purified by flash column chromatograph to give the pure products. The

products were characterized by 1H NMR, 13C NMR, LC-MS.

5. Control Experiments.

Ph

PhF N

SO2Ph

SO2Ph

+ Standard conditions

24

Ph

Ph

NSO2Ph

SO2Ph

5

Can not be detected by LC-MS

Ph

PhN

SO2Ph

N

+

6

OH

NN

S OO

NSO2PhN

H3a, 57%

NSO2PhN

F7

Ni(OAc)2•4H2O (10 mol %)Na2CO3 (2.0 equiv)

DMF, 50 °C2.0 equiv BHT

+

(2)

(1)

8

The mass of 8

6. X-Ray Crystallographic Data of 3a

The structure of 3a (CCDC 1873672) was determined by the X-ray diffraction.

5

Recrystallized from CH2Cl2. Further information can be found in the CIF file.1

6

7. Plausible Mechanism.

N NSO

O Ph

F

N

O-H

NSO

O PhF

S OO

Ph

Na2CO3

N N S

O

O

PhFO

SO

O

Ph

H

PhSO3Na

++ N

O

H+

S

O-O

N

PhSO

O Ph

F

N NSO

O Ph

Ni(II)AcO

F

N NSO

O Ph

NH

NSO

O Ph

N O

N NH

SO

O Ph

N O

F

N O

HF N O+

1 2 AB

C

7

7

Ni(I)-OAc

H2ON O

Ni(I)-OAc

F

F3

E

Path X

Path YG

DMF

D

F

H

D

I

J

F

tautomerization

8. Characterization data of the products.

(E)-N-(quinolin-2(1H)-ylidene)benzenesulfonamidetert-butyl (3a): (65.6 mg, yield

77 %); White solid; m.p. 162-164 °C.

NH

NSO

O

1H NMR (400 MHz, CDCl3, ppm) δ: 12.00 (s, 1H), 7.99-8.01 (m, 2H), 7.88 (d, J = 9.5

Hz, 1H), 7.59-7.62 (m, 2H), 7.42-7.53 (m, 4H), 7.32-7.36 (m, 1H), 7.07 (d, J = 9.3 Hz,

1H); 13C NMR (100 MHz, CDCl3, ppm) δ: 154.5, 142.8, 140.9, 136.4, 132.1, 131.8,

128.8, 128.2, 126.2, 124.8, 121.4, 120.9, 117.4. HRMS (ESI): m/z calcd for

C15H12N2O2S [M+H]+: 285.0692, found: 285.0699.

7

(E)-N-(4-methylquinolin-2(1H)-ylidene)benzenesulfonamide (3b): (67.9 mg, yield

76 %); White solid; m.p. 202-204 °C.

NH

NSO

O


Hz, 1H), 7.60-7.64 (m, 1H), 7.43-7.52 (m, 4H), 7.37-7.41 (m, 1H), 6.82 (s, 1H); 2.54

(s, 3H); 13C NMR (100 MHz, CDCl3, ppm) δ: 154.2, 150.2, 143.1, 136.1, 131.9, 131.6,

128.8, 126.2, 124.6, 122.0, 119.8, 117.7, 19.3. HRMS (ESI): m/z calcd for

C16H14N2O2S [M+H]+: 299.0849, found: 299.0854.

(E)-N-(4-ethylquinolin-2(1H)-ylidene)benzenesulfonamide (3c): (48.7 mg, yield 52

%); White solid; m.p. 192-193 °C.

NH

NSO

O


Hz, 1H), 7.59-7.63 (m, 1H), 7.44-7.50 (m, 4H), 7.35-7.40 (m, 1H), 6.84 (s, 1H); 2.93

(t, J = 7.3 Hz, 2H), 1.33 (t, J = 7.5 Hz, 3H); 13C NMR (100 MHz, CDCl3, ppm) δ:

155.3, 154.3, 143.1, 136.2, 131.9, 131.4, 128.8, 126.2, 124.6, 124.2, 121.3, 118.2,

117.8, 25.3, 12.8. HRMS (ESI): m/z calcd for C17H16N2O2S [M+H]+: 313.1005, found:

313.1010.

(E)-N-(4-propylquinolin-2(1H)-ylidene)benzenesulfonamide (3d): (52.8 mg, yield

54 %); White solid; m.p. 210-211 °C.

NH

NSO

O


Hz, 1H), 7.59-7.63 (t, 1H), 7.44-7.53 (m, 4H), 7.36-7.39 (m, 1H), 6.80 (s, 1H); 2.86 (t,

J = 7.4 Hz, 2H), 1.69-1.78 (m, 2H), 1.03 (t, J = 7.4 Hz, 3H); 13C NMR (100 MHz,

8

CDCl3, ppm) δ: 154.2, 154.0, 143.1, 136.4, 131.9, 131.4, 128.8, 126.2, 124.6, 124.4,

121.4, 119.0, 118.0, 34.4, 22.1, 14.0. HRMS (ESI): m/z calcd for C18H18N2O2S

[M+H]+: 327.1162, found: 327.1166.

(E)-N-(4-cyclopropylquinolin-2(1H)-ylidene)benzenesulfonamide (3e): (58.3 mg,

yield 60 %); yellow solid; m.p. 204-206 °C.

NH

NSO

O

1H NMR (400 MHz, CDCl3, ppm) δ: 11.83 (s, 1H), 8.10 (d, J = 7.8 Hz, 1H), 7.98-

8.00 (m, 2H), 7.60-7.64 (m, 1H), 7.38-7.52 (m, 5H), 6.56 (s, 1H), 2.18-2.25 (m, 1H),

1.13-1.18 (m, 2H), 0.81-0.85 (m, 2H); 13C NMR (100 MHz, CDCl3, ppm) δ: 155.3,

154.4, 143.1, 136.0, 131.9, 131.5, 128.8, 126.2, 124.8, 124.6, 122.4, 117.6, 116.1,

12.6, 8.2. HRMS (ESI): m/z calcd for C18H16N2O2S [M+H]+: 325.1005, found:

325.1009.

(E)-N-(4-benzylquinolin-2(1H)-ylidene)benzenesulfonamide (3f): (65.1 mg, yield

58 %); White solid; m.p. 219-220 °C.

NH

NSO

O

Ph


Hz, 1H), 7.58-7.62 (m, 1H), 7.43-7.53 (m, 4H), 7.24-7.36 (m, 4H), 7.18-7.19 (like d,

2H), 6.64 (s, 1H), 4.22 (s, 2H); 13C NMR (100 MHz, CDCl3, ppm) δ: 154.0, 152.1,

142.9, 136.5, 136.3, 132.0, 131.5, 129.1, 129.0, 128.8, 127.2, 126.2, 124.7, 121.3,

121.0, 117.7, 38.5. HRMS (ESI): m/z calcd for C22H18N2O2S [M+H]+: 375.1162,

found: 375.1165.

(E)-N-(3-methylquinolin-2(1H)-ylidene)benzenesulfonamide (3g): (59.0 mg, yield

66 %); White solid; m.p. 160-162 °C.

NH

NSO

O

9

1H NMR (400 MHz, CDCl3, ppm) δ: 12.12 (s, 1H), 8.01-8.03 (m, 2H), 7.73 (s, 1H),

7.44-7.56 (m, 5H), 7.30-7.36 (m, 2H), 2.24 (s, 3H); 13C NMR (100 MHz, CDCl3, ppm)

δ: 154.1, 143.3, 138.4, 135.0, 132.0, 130.5, 130.1, 128.7, 127.3, 126.0, 124.6, 121.3,

116.5, 18.0. HRMS (ESI): m/z calcd for C16H14N2O2S [M+H]+: 299.0849, found:

299.0854.

(E)-N-(6-methylquinolin-2(1H)-ylidene)benzenesulfonamide (3h): (68.8 mg, yield

77 %); White solid; m.p. 175-177 °C.

NH

NSO

O


Hz, 1H), 7.36-7.52 (m, 6H), 6.94 (d, J = 9.4 Hz, 1H), 2.45 (s, 3H); 13C NMR (100

MHz, CDCl3, ppm) δ: 154.3, 143.0, 140.8, 134.8, 134.6, 133.4, 132.0, 128.8, 127.6,

126.2, 121.5, 120.5, 117.2, 21.0. HRMS (ESI): m/z calcd for C16H14N2O2S [M+H]+:

299.0849, found: 299.0852.

(E)-N-(7-ethylquinolin-2(1H)-ylidene)benzenesulfonamide (3i): (65.5 mg, yield 70

%); White solid; m.p. 139-141 °C.

NH

NSO

O


Hz, 1H), 7.53 (d, J = 8.2 Hz, 2H), 7.42-7.49 (m, 3H), 7.37 (s, 1H), 7.2 (dd, J1 = 1.2

Hz, J2 = 8.2, 1H); 7.03 (d, J = 9.3 Hz, 1H), 2.78 (q, J = 7.6 Hz, 2H), 1.29 (t, J = 7.6

Hz, 3H). 13C NMR (100 MHz, CDCl3, ppm) δ: 154.8, 149.3, 143.1, 141.0, 136.7,

132.0, 128.8, 127.9, 126.2, 125.5, 119.6, 119.2, 116.0, 29.1, 15.1. HRMS (ESI): m/z

calcd for C17H16N2O2S [M+H]+: 313.1005, found: 313.1013.

(E)-N-(4-phenylquinolin-2(1H)-ylidene)benzenesulfonamide (3j): (86.4 mg, yield

80 %); White solid; m.p. 200-202 °C.

NH

NSO

O

Ph

10

1H NMR (400 MHz, CDCl3, ppm) δ: 11.98 (s, 1H), 8.02-8.04 (m, 2H), 7.61-7.66 (m,

2H), 7.45-7.54 (m, 7H), 7.40-7.43 (m, 2H), 7.29-7.33 (m, 1H), 6.92 (s, 1H); 13C NMR

(100 MHz, CDCl3, ppm) δ: 153.8, 153.6, 143.0, 136.8, 136.2, 132.0, 131.7, 129.4,

128.9, 128.8, 127.1, 126.3, 124.6, 121.0, 120.6, 117.7. HRMS (ESI): m/z calcd for

C21H16N2O2S [M+H]+: 361.1005, found: 361.1013.

(E)-N-(6-phenylquinolin-2(1H)-ylidene)benzenesulfonamide (3k): (49.7 mg, yield

46 %); White solid; m.p. 180-182 °C.

NH

NSO

OPh


Hz, 1H), 7.85-7.88 (m, 1H), 7.80-7.81 (like d, 1H), 7.57-7.62 (m, 3H), 7.45-7.52 (m,

5H), 7.38-7.42 (m, 1H), 7.06 (d, J = 9.4 Hz, 1H); 13C NMR (100 MHz, CDCl3, ppm)

δ: 154.4, 142.8, 141.0, 139.3, 138.1, 135.8, 132.1, 131.1, 129.1, 128.8, 127.9, 127.1,


361.1005, found: 361.1010.

(E)-N-(4-(4-(tert-butyl)phenyl)quinolin-2(1H)-ylidene)benzenesulfonamide (3l):

(91.1 mg, yield 73 %); White solid; m.p. 214-216 °C.

NH

NSO

O


Hz, 1H), 7.61-7.65 (m, 1H), 7.45-7.53 (m, 6H), 7.35-7.37 (like d, 2H), 7.29-7.33 (m,


152.7, 143.1, 137.0, 133.3, 132.0, 131.7, 128.8, 128.7, 127.2, 126.3, 125.8, 124.6,


417.1631, found: 417.1641.

(E)-N-(5-bromoquinolin-2(1H)-ylidene)benzenesulfonamide (3m): (54.3 mg, yield

11

50 %); White solid; m.p. 185-187 °C.

NH

NSO

O

Br


8.02 (m, 2H), 7.58-7.60 (m, 1H), 7.42-7.55 (m, 5H), 7.12 (d, J = 9.7 Hz, 1H); 13C

NMR (100 MHz, CDCl3, ppm) δ: 153.9, 142.3, 139.6, 138.3, 132.4, 132.0, 128.9,

128.7, 126.4, 122.9, 121.5, 121.0, 117.7. HRMS (ESI): m/z calcd for C15H11BrN2O2S

[M+H]+: 362.9797, found: 362.9800.

(E)-N-(6-bromoquinolin-2(1H)-ylidene)benzenesulfonamide (3n): (82.5 mg, yield

76 %); White solid; m.p. 186-188 °C.

NH

NSO

OBr


2H), 7.68-7.70 (m, 1H), 7.45-7.55 (m, 3H), 7.40 (d, J = 8.8 Hz, 1H), 7.04 (d, J = 9.5

Hz, 1H); 13C NMR (100 MHz, CDCl3, ppm) δ: 154.1, 142.3, 139.5, 135.9, 134.7,


C15H11BrN2O2S [M+H]+: 362.9797, found: 362.9799.

(E)-N-(7-bromoquinolin-2(1H)-ylidene)benzenesulfonamide (3o): (79.3 mg, yield

73 %); White solid; m.p. 173-174 °C.

NH

NSO

O

Br

1H NMR (400 MHz, CDCl3, ppm) δ: 11.72 (s, 1H), 7.99-8.01 (like d, 2H), 7.83 (d, J =

9.4 Hz, 1H), 7.69 (s, 1H), 7.52-7.46 (m, 5H), 7.06 (d, J = 9.3 Hz, 1H); 13C NMR (100

MHz, CDCl3, ppm) δ: 154.2, 142.3, 140.3, 137.8, 132.3, 129.2, 128.9, 128.2, 126.4,

126.0, 120.6, 120.4, 120.3. HRMS (ESI): m/z calcd for C15H11BrN2O2S [M+H]+:

362.9797, found: 362.9799..

(E)-N-(4-chloroquinolin-2(1H)-ylidene)benzenesulfonamide (3p): (58.2 mg, yield

61 %); White solid; m.p. 160-162 °C.

12

NH

NSO

O

Cl


1H), 7.51-7.55 (m, 2H), 7.42-7.49 (m, 3H), 7.24 (s, 1H); 13C NMR (100 MHz, CDCl3,

ppm) δ: 153.6, 147.0, 142.5, 137.2, 132.9, 132.3, 128.9, 126.3, 125.3, 125.3, 120.2,

119.0, 118.1. HRMS (ESI): m/z calcd for C15H11ClN2O2S [M+H]+: 319.0303, found:

319.0307.

(E)-N-(5-chloroquinolin-2(1H)-ylidene)benzenesulfonamide (3q): (57.2 mg, yield

60 %); White solid; m.p. 184-186 °C.

NH

NSO

O

Cl


8.01 (m, 2H), 7.43-7.53 (m, 5H), 7.38 (dd, J1 = 1.6 Hz, J2 = 7.1 Hz, 1H), 7.19 (d, J =

9.6 Hz, 1H); 13C NMR (100 MHz, CDCl3, ppm) δ: 154.0, 142.3, 138.1, 137.1, 132.7,


C15H11ClN2O2S [M+H]+: 319.0303, found: 319.0307.

(E)-N-(4-methyl-7-(trifluoromethyl)quinolin-2(1H)-ylidene)benzenesulfonamide

(3t): (68.1 mg, yield 62 %); White solid; m.p. 185-187 °C.

NH

NSO

O

F3C

1H NMR (400 MHz, CDCl3, ppm) δ: 11.72 (s, 1H), 7.98-8.00 (like d, 2H), 7.86 (d, J =

8.4 Hz, 1H), 7.76 (s, 1H), 7.57 (d, J = 8.4 Hz, 1H), 7.43-7.52 (m, 3H), 6.99 (s, 1H),

2.56 (s, 3H); 13C NMR (100 MHz, CDCl3, ppm) δ: 154.0, 149.1, 142.4, 136.5, 133.0

(q, J = 32.8 Hz), 132.3, 128.8, 126.3, 125.7, 124.2, 123.2 (q, J = 273.5 Hz), 121.7,

120.7 (q, J = 3.1 Hz), 115.6 (q, J = 4.2 Hz), 19.2. HRMS (ESI): m/z calcd for

C17H13F3N2O2S [M+H]+: 367.0723, found: 367.0726.

(E)-N-(4-chloro-7-methoxyquinolin-2(1H)-ylidene)benzenesulfonamide (3v):

13

(57.4 mg, yield 55 %); White solid; m.p. 188-190 °C.

NH

NSO

O

Cl

O


Hz, 1H), 7.49-7.53 (m, 1H), 7.41-7.46 (m, 3H), 7.33 (d, J = 1.9 Hz, 1H), 7.00 (dd, J1

= 2.2 Hz, J2 = 9.1 Hz, 1H), 3.95 (s, 3H); 13C NMR (100 MHz, CDCl3, ppm) δ: 163.8,

154.9, 147.7, 142.7, 139.5, 132.1, 128.9, 126.6, 126.3, 116.5, 114.7, 114.6, 99.6, 56.4.

HRMS (ESI): m/z calcd for C16H13ClN2O3S [M+H]+: 349.0408, found: 349.0411.

N-(isoquinolin-1-yl)benzenesulfonamide (3w): (6.0 mg, yield 7 %); White solid;

m.p. 62-63 °C.

N

NHS

O

O


8.05 (m, 2H), 7.71-7.75 (m, 1H), 7.44-7.59 (m, 5H), 7.21-7.24 (m, 1H), 6.83 (d, J =

7.0 Hz 1H); 13C NMR (100 MHz, CDCl3, ppm) δ: 154.1, 143.3, 136.8, 133.7, 131.9,


C15H12N2O2S [M+H]+: 285.0692, found: 285.0694.

N-fluoro-N-(quinolin-2-yl)benzenesulfonamide (7): (47.1 mg, yield 52 %); faint

yellow solid; m.p. 187-189 °C.

N NSO

O

F

1H NMR (400 MHz, MeOD, ppm) δ: 8.35 (d, J = 8.8 Hz, 1H), 7.91 (d, J = 8.1 Hz,

1H), 7.83 (d, J = 8.5 Hz, 1H), 7.69-7.75 (m, 2H), 7.65 (d, J = 7.5 Hz, 2H), 7.60 (t, J =

7.2 Hz, 1H), 7.47-7.51 (m, 2H), 7.35 (d, J = 8.5 Hz, 1H); 13C NMR (100 MHz, MeOD,

ppm) δ: 152.8 (d, J = 8.7 Hz), 147.4, 140.5 (d, J = 2.6 Hz), 136.7, 133.3, 132.1, 131.0,

130.4, 129.5, 129.2, 129.1, 129.0, 116.4 (d, J = 5.2 Hz). 19F NMR (376 MHz, MeOD,

14

ppm) δ = -49.0; HRMS (ESI): m/z calcd for C15H11FN2O2S [M+H]+: 303.0598, found:

303.0599.

N-(3,5-di-tert-butyl-4-hydroxybenzyl)-N-(quinolin-2-yl)benzenesulfonamide (8):

White solid; m.p. 67-69 °C.

OH

NN

S OO

1H NMR (400 MHz, CDCl3, ppm) δ: 8.00 (d, J = 9.6 Hz, 1H), 7.91 (d, J = 7.4 Hz, 2H),

7.86 (d, J = 9.6 Hz, 1H), 7.57-7.67 (m, 3H), 7.32-7.46 (m, 4H), 7.02 (s, 2H), 5.68 (s,


143.8, 139.6, 139.0, 136.2, 131.9, 131.4, 129.2, 128.5, 126.3, 125.6, 123.9, 123.8,

122.1, 117.4, 116.5, 49.1, 34.3, 30.2. LC-MS (ESI, m/z): [M+Na]+ 525.3.

9. References

1. (a) A. Londregan, K. Burford, E. Conn, K. Hesp, Org. Lett. 2014, 16, 3336-3339.

(b) A. Biswas, U. Karmakar, S. Nandi, R. Samanta, J. Org. Chem. 2017, 82, 8933-

8942.

15

10. 1H NMR and 13C NMR spectra of the products1H NMR and 13C NMR of compound 3a

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

7.058

7.081

7.260

7.321

7.323

7.341

7.359

7.361

7.418

7.421

7.438

7.458

7.475

7.487

7.493

7.501

7.513

7.535

7.587

7.604

7.623

7.864

7.888

7.990

7.993

8.011

12.002

1.000

1.039

4.046

2.095

1.065

2.008

0.849

1HCDCl3

NH

NSO

O

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

117.356

120.888

121.417

124.813

126.244

128.153

128.811

131.826

132.091

136.418

140.923

142.825

154.451

13CCDCl3

NH

NSO

O

16

1H NMR and 13C NMR of compound 3b

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

2.540

2.542

6.823

7.260

7.366

7.369

7.386

7.404

7.407

7.433

7.438

7.442

7.455

7.474

7.484

7.487

7.491

7.498

7.505

7.514

7.520

7.523

7.601

7.604

7.622

7.640

7.643

7.745

7.747

7.765

7.987

7.991

8.008

8.011

11.839

3.020

0.976

1.025

3.993

1.026

1.024

2.000

0.979

1HCDCl3

NH

NSO

O

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

19.296

117.700

119.767

121.957

124.646

126.177

128.759

131.618

131.902

136.110

143.146

150.210

154.206

13CCDCl3

NH

NSO

O

17

1H NMR and 13C NMR of compound 3c

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

1.310

1.329

1.347

2.902

2.903

2.920

2.921

2.938

2.940

2.957

6.840

7.260

7.354

7.357

7.375

7.393

7.395

7.436

7.440

7.445

7.457

7.461

7.473

7.476

7.483

7.487

7.491

7.497

7.504

7.587

7.590

7.607

7.625

7.628

7.785

7.805

8.002

8.006

8.023

11.899

3.067

1.994

0.950

1.078

4.026

1.076

1.000

2.056

0.976

1HCDCl3

NH

NSO

O

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

12.824

25.296

117.841

118.173

121.274

124.203

124.610

126.214

128.765

131.419

131.926

136.218

143.127

154.324

155.312

13CCDCl3

NH

NSO

O

18

1H NMR and 13C NMR of compound 3d

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

1.028

1.046

1.689

1.707

1.726

1.745

1.764

1.782

2.836

2.856

2.875

6.803

7.260

7.356

7.374

7.393

7.394

7.440

7.461

7.480

7.487

7.492

7.495

7.502

7.509

7.518

7.524

7.527

7.590

7.592

7.610

7.628

7.630

7.785

7.804

7.995

7.999

8.016

8.018

11.877

2.992

2.022

1.994

0.987

1.033

4.089

1.073

0.986

2.000

1.011

1HCDCl3

NH

NSO

O

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

13.985

22.123

34.355

117.933

118.950

121.361

124.398

124.564

126.215

128.754

131.433

131.904

136.389

143.138

154.045

154.218

13CCDCl3

NH

NSO

O

19

1H NMR and 13C NMR of compound 3e

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

0.813

0.825

0.829

0.839

0.842

0.854

1.127

1.138

1.143

1.147

1.159

1.163

1.175

2.197

2.205

2.218

2.231

2.238

6.559

7.260

7.383

7.385

7.403

7.423

7.436

7.442

7.457

7.476

7.483

7.487

7.490

7.498

7.504

7.520

7.523

7.603

7.605

7.623

7.641

7.644

7.983

7.987

8.004

8.083

8.103

2.014

2.011

0.986

0.973

5.020

1.069

1.996

1.000

0.996

1HCDCl3

NH

NSO

O

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

8.217

12.608

116.107

117.573

122.396

124.578

124.788

126.180

128.769

131.473

131.937

135.955

143.111

154.360

155.322

13CCDCl3

NH

NSO

O

20

1H NMR and 13C NMR of compound 3f

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

0.000

4.220

6.643

7.175

7.193

7.241

7.259

7.277

7.301

7.320

7.337

7.357

7.433

7.451

7.470

7.489

7.501

7.507

7.514

7.525

7.581

7.599

7.618

7.620

7.804

7.824

7.955

7.959

7.976

11.851

2.070

1.000

2.044

4.370

4.118

1.086

1.014

1.994

0.882

1HCDCl3

NH

NSO

O

Ph

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

38.515

117.749

121.013

121.265

124.706

126.249

127.189

128.783

128.999

129.065

131.498

132.015

136.342

136.545

142.872

152.135

153.974

13CCDCl3

NH

NSO

O

Ph

21

1H NMR and 13C NMR of compound 3g

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

0.000

2.244

7.270

7.298

7.316

7.337

7.338

7.360

7.439

7.443

7.447

7.460

7.479

7.485

7.489

7.492

7.500

7.507

7.513

7.532

7.539

7.552

7.559

7.731

8.007

8.011

8.028

12.121

3.004

1.991

5.049

1.000

1.978

1.016

1HCDCl3

NH

NSO

O

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

17.954

116.515

121.302

124.599

126.039

127.327

128.745

130.148

130.482

131.955

134.962

138.376

143.267

154.052

13CCDCl3

NH

NSO

O

22

1H NMR and 13C NMR of compound 3h

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

2.447

6.933

6.956

7.359

7.380

7.408

7.433

7.438

7.443

7.456

7.471

7.474

7.480

7.485

7.489

7.493

7.500

7.507

7.525

7.803

7.826

7.988

7.992

7.997

8.005

8.009

8.012

11.922

3.089

1.000

6.077

1.033

2.019

0.594

1HCDCl3

NH

NSO

O

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

21.002

117.246

120.477

121.498

126.225

127.591

128.779

131.984

133.375

134.583

134.787

140.764

142.976

154.286

13CCDCl3

NH

NSO

O

23

1H NMR and 13C NMR of compound 3i

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

0.000

1.275

1.294

1.313

2.752

2.771

2.790

2.809

7.016

7.040

7.190

7.193

7.210

7.213

7.271

7.374

7.418

7.422

7.426

7.439

7.443

7.458

7.470

7.474

7.478

7.485

7.492

7.521

7.541

7.845

7.869

8.000

8.004

8.009

8.017

8.021

8.024

12.077

3.055

2.061

1.000

1.028

1.017

3.099

1.008

1.033

2.016

1.024

1HCDCl3

NH

NSO

O

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

15.093

29.115

116.016

119.207

119.620

125.492

126.229

127.930

128.768

131.954

136.741

141.007

143.051

149.306

154.805

13CCDCl3

NH

NSO

O

24

1H NMR and 13C NMR of compound 3j

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

6.917

7.260

7.287

7.290

7.305

7.309

7.325

7.328

7.401

7.408

7.413

7.417

7.422

7.425

7.436

7.450

7.455

7.459

7.472

7.475

7.491

7.501

7.504

7.508

7.517

7.530

7.537

7.615

7.618

7.637

7.656

8.017

8.021

8.026

8.034

8.038

8.041

11.981

0.941

1.029

2.000

7.175

2.080

2.000

1.007

1HCDCl3

NH

NSO

O

Ph

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

117.683

120.585

121.024

124.644

126.263

127.062

128.808

128.847

129.389

131.696

132.039

136.172

136.842

142.978

153.581

153.812

13CCDCl3

NH

NSO

O

Ph

25

1H NMR and 13C NMR of compound 3k

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

0.000

7.045

7.069

7.260

7.379

7.397

7.415

7.454

7.462

7.471

7.481

7.490

7.500

7.505

7.523

7.572

7.598

7.618

7.809

7.813

7.854

7.859

7.876

7.880

7.926

7.949

8.014

8.017

8.034

12.021

1.000

1.073

5.009

3.031

1.022

1.031

1.039

2.018

0.996

1HCDCl3

NH

NSO

OPh

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

117.948

120.996

121.796

126.008

126.282

127.100

127.950

128.840

129.102

131.079

132.126

135.799

138.071

139.329

141.042

142.804

154.375

13CCDCl3

NH

NSO

OPh

26

1H NMR and 13C NMR of compound 3l

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

0.000

7.261

7.281

7.291

7.301

7.311

7.321

7.349

7.369

7.434

7.451

7.470

7.485

7.503

7.515

7.535

7.619

7.628

7.708

7.728

8.020

8.038

12.154

9.025

1.000

1.030

2.056

5.071

2.056

1.030

2.032

1.054

1HCDCl3

NH

NSO

O

t-Bu

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

31.301

34.846

117.842

119.694

121.118

124.576

125.761

126.296

127.161

128.712

128.776

131.698

131.953

133.266

137.019

143.101

152.711

153.866

154.170

13CCDCl3

NH

NSO

O

t-Bu

27

1H NMR and 13C NMR of compound 3m

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

0.000

7.107

7.131

7.265

7.423

7.444

7.461

7.473

7.492

7.515

7.532

7.551

7.581

7.585

7.597

7.602

7.996

7.999

8.017

8.230

8.254

11.774

1.000

5.046

0.984

1.990

1.016

0.984

1HCDCl3

NH

NSO

O

Br

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

117.660

121.048

121.469

122.910

126.373

128.653

128.890

132.044

132.356

138.267

139.623

142.285

153.949

13CCDCl3

NH

NSO

O

Br

28

1H NMR and 13C NMR of compound 3n

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

7.024

7.048

7.260

7.390

7.412

7.450

7.453

7.457

7.471

7.475

7.487

7.490

7.510

7.514

7.517

7.526

7.532

7.539

7.547

7.550

7.553

7.679

7.684

7.701

7.706

7.768

7.774

7.778

7.801

7.981

7.985

7.990

7.998

8.002

8.005

11.814

0.991

1.005

3.092

1.023

2.047

2.000

0.996

1HCDCl3

NH

NSO

OBr

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

117.699

119.557

121.310

122.876

126.352

128.878

130.255

132.315

134.684

135.881

139.548

142.358

154.082

13CCDCl3

NH

NSO

OBr

29

1H NMR and 13C NMR of compound 3o

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

0.000

7.050

7.073

7.267

7.462

7.471

7.481

7.491

7.504

7.522

7.691

7.819

7.843

7.989

8.007

11.719

1.000

5.062

1.030

1.061

2.017

0.989

1HCDCl3

NH

NSO

O

Br

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

120.300

120.430

120.635

126.003

126.371

128.240

128.876

129.242

132.310

137.816

140.269

142.348

154.213

13CCDCl3

NH

NSO

O

Br

30

1H NMR and 13C NMR of compound 3p

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

0.000

7.237

7.264

7.418

7.420

7.438

7.445

7.448

7.456

7.458

7.466

7.469

7.485

7.509

7.512

7.527

7.534

7.554

7.664

7.667

7.685

7.702

7.705

7.982

7.986

7.992

7.995

8.003

8.012

8.015

11.852

1.000

3.004

2.085

1.061

3.067

0.960

1HCDCl3

NH

NSO

O

Cl

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

118.093

119.047

120.176

125.311

125.331

126.325

128.882

132.266

132.949

137.154

142.467

147.009

153.641

13CCDCl3

NH

NSO

O

Cl

31

1H NMR and 13C NMR of compound 3q

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

7.177

7.201

7.260

7.369

7.373

7.387

7.391

7.433

7.436

7.440

7.454

7.457

7.470

7.473

7.485

7.488

7.493

7.497

7.511

7.515

7.523

7.532

7.985

7.988

8.006

8.251

8.275

11.929

1.004

1.005

5.146

2.037

1.000

1.015

1HCDCl3

NH

NSO

O

Cl

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

116.902

119.634

121.381

125.122

126.396

128.903

131.753

132.354

132.741

137.081

138.120

142.302

153.993

13CCDCl3

NH

NSO

O

Cl

32

1H NMR and 13C NMR of compound 3t

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

2.557

6.991

7.260

7.430

7.447

7.467

7.488

7.506

7.524

7.555

7.576

7.763

7.848

7.869

7.982

8.000

11.727

3.071

1.000

3.050

1.026

1.116

1.075

2.075

0.899

1HCDCl3

NH

NSO

O

F3C

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

19.246

115.607

115.647

119.207

120.688

120.719

121.650

121.920

124.159

124.632

125.687

126.310

128.846

132.268

132.537

132.866

133.199

133.528

136.510

142.430

149.052

153.987

13CCDCl3

NH

NSO

O

F3C

33

1H NMR and 13C NMR of compound 3v

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

0.000

3.952

6.991

6.996

7.013

7.019

7.265

7.330

7.413

7.426

7.444

7.463

7.493

7.511

7.529

7.847

7.870

7.975

7.994

12.444

3.056

1.000

1.033

3.017

1.058

1.030

2.030

1.024

1HCDCl3

NH

NSO

O

Cl

O

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

56.370

99.573

114.628

116.536

126.333

126.585

128.854

132.109

139.491

142.699

147.709

154.892

163.814

13CCDCl3

NH

NSO

O

Cl

O

34

1H NMR and 13C NMR of compound 3w

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

6.822

6.839

7.212

7.227

7.229

7.244

7.260

7.444

7.449

7.454

7.466

7.482

7.485

7.491

7.495

7.499

7.506

7.513

7.521

7.523

7.531

7.541

7.559

7.562

7.574

7.594

7.712

7.715

7.732

7.749

7.752

8.025

8.029

8.034

8.042

8.046

8.049

8.574

8.595

0.995

1.001

5.099

1.094

1.984

1.000

1.015

1HCDCl3

N

NHS

O

O

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

110.627

124.770

125.990

126.060

126.365

127.929

128.045

128.754

131.934

133.695

136.816

143.269

154.059

13CCDCl3

N

NHS

O

O

35

1H NMR, 13C NMR and 19F NMR of compound 7

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

3.310

4.863

7.344

7.366

7.467

7.487

7.506

7.582

7.600

7.619

7.637

7.656

7.694

7.713

7.733

7.753

7.819

7.840

7.904

7.925

8.337

8.359

1.001

2.064

3.051

2.095

1.049

1.036

1.000

1HMeOD

N NSO

O

F

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

116.383

116.435

129.007

129.050

129.178

129.522

130.449

131.048

132.128

133.305

136.735

140.514

140.540

147.430

152.779

152.865

13CMeOD

N NSO

O

F

36

-180-160-140-120-100-80-60-40-200 ppm

-48.956

19FMeOD

N NSO

O

F

1H NMR and 13C NMR of compound 8

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

1.325

5.163

5.682

7.022

7.260

7.317

7.335

7.356

7.377

7.396

7.425

7.443

7.462

7.575

7.595

7.614

7.629

7.652

7.672

7.848

7.872

7.898

7.917

7.987

8.011

18.045

1.040

2.000

2.095

4.157

3.072

1.063

1.946

1.064

1HCDCl3

OH

NN

S OO

37

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

30.152

34.278

49.079

116.511

117.386

122.094

123.828

123.904

125.640

126.288

128.526

129.241

131.392

131.917

136.243

139.040

139.601

143.832

153.201

156.086

13CCDCl3

OH

NN

S OO

efficient synthesis of diarymethane derivatives by pdcl2

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